The present invention relates to compositions useful as a protectant for automotive surfaces including painted, vinyl, chrome, and glass surfaces, as well as other vehicles such as motorcycles, trucks, boats, RVs, or stationary articles, as well as many other hard surface found around the home or garage including glass surfaces. The protectant has several unique features, such as containing UV protectants, and durability. It is water-based, abrasive-free, and virtually free of organic solvents. Furthermore, the compositions are in the form of liquid that can be sprayed onto a surface by means of a pump spray or aerosol. The compositions are easily applied onto painted or glass surfaces and can be applied to wet or dry surfaces, with minimal wiping, leaving a dust-free, streak-free, glossy finish.
Traditionally, the steps in waxing/polishing an automobile have been (1) wash the car, (2) dry the car, (3) apply and buff the wax/polish, (4) allow the wax/polish to dry, (5) remove powdery residue from the surface. In contrast, the steps in using the protectant of this invention are simply (1) wash the car, (2) spray protectant onto the wet car and dry the car. The protectant requires no further effort such as buffing and there is no powdery residue to remove. The drying of the car is enough to level the protectant of this invention to a streak-free, glossy finish. Therefore, this is the only wax-containing product that does not require abrasives and does not leave dried residues that need to be removed.
In the past, polishes have required one or more abrasives to level the wax film when it is being applied and during buffing. If the abrasive is eliminated, the result has been a smeary or streaked appearance on the surface. Furthermore, as the solvents evaporate in these types of products, most of the wax and other hydrophobic components such as silicone compounds, are extracted into the dried powdery residue and trapped there. Therefore, wiping off the dried on residues removes much of the wax and other actives in these products. Furthermore, UV protectants could not be effectively incorporated in these products since much of the UV absorbers would be trapped into the residues that are wiped off.
U.S. Pat. No. 5,288,314 discloses a polish for cleaning metallic and fiberglass surfaces, such as automobile, truck and boat bodies, and for providing a protective film on the surface. The polish comprises water in an amount between about 40.0 to about 75.0 percent, a solvent in an amount between about 12.0 to about 35.0 percent, a rheological additive in an amount between about 0.30 to about 1.0 percent, an ultraviolet light absorber in an amount between about 0.05 to about 0.50 percent, a dye in an amount between about 0.0005 to about 3.0 percent, a first silicate in an amount between about 5.0 to about 15.0 percent, dimethylpolysiloxane in an amount between about 0.50 to about 6.0 percent, a silicone resin solution in an amount between about 0.10 to about 3.0 percent, oleic diethanol amide in an amount between about 0.50 to about 2.0 percent, a second silicate in an amount between about 0.10 to about 3.0 percent, and a bactericide in an amount between about 0.05 to about 0.20 percent, by weight of the total polish.
In addition to the effort involved in removing the dried film of such compositions, there are other disadvantages. Paint technology has changed significantly and at present, abrasives are in many cases too aggressive and tend to scratch the painted surface. However, simply removing the abrasives from formulations is not a viable alternative. Abrasives aid in the even distribution of wax and silicone film forming components thereby reducing the tendency to streak. Removing them tends to increase streaking which is not desirable from a consumer""s point of view. Furthermore, much of the active components including the ultraviolet absorbers would be lost in the process of removing the residues.
A great deal of research has gone into developing polish compositions that are free from abrasives yet do not streak or smear.
U.S. Pat. No. 5,700,312 discloses an auto finish-treating composition universally useful on paint, metal, vinyl and other plastic finishes comprising of micronized wax dispersed in a water/organic solvent emulsion also containing silicone liquid emulsified in both the organic and aqueous phases.
U.S. Pat. No. 5,882,387 discloses a wipe-on polish composition for automotive surfaces which contains no wax or abrasive components. The polish requires minimal effort to wipe out to a thin, glossy, streak-free, hydrophobic film. The polish is comprised of an emulsion that contains an organopolysiloxane and a volatile diluent.
U.S. Pat. No. 5,913,969 discloses a protective composition for automotive painted surfaces. The polish is comprised of emulsified silicone, an evaporation modifier and an agent, which increases wetting speed, dispersed in water.
Such micronized wax formulation and the polish formulations mentioned above lack durability and usually last for a few weeks only. Furthermore, since micronized wax or silicone oils are not film formers, UV protectants cannot be effectively incorporated in such products.
In view of these problems there is a need for a wax-based protectant that is substantially abrasives-free that does not smear or streak. Furthermore, UV protectants can be effectively incorporated in such a wax protectant to offer protection against sun damage.
It is one object of the present invention to provide a wax-based protectant composition, that is abrasive-free and therefore non-damaging to the clear coat type finishes, which provides protection to a substrate from sources of environmental damage. The sources of environmental damage can include for example, water, rain, acid rain, inorganic salts, dirt, grime, road tar, bird droppings and other environmental contaminants.
It is another object of the present invention to provide a composition that provides protection and screen from sunlight and UV rays to the substrate it is applied to. The UV absorbers and/or UV light stabilizers used in the present invention are hydrophobic in nature and are encapsulated in the wax particles.
It is another object of the present invention to provide a composition that leaves no residue. Therefore, substantial amounts of the wax, UV protectants, and other active components are left on the surface of the substrate. Furthermore, the protectant is very easy to apply since there is no buffing required and there are no powdery residues to remove.
It is another object of the present invention to provide a composition that can be applied to wet or dry surfaces and then wiped dry with no buffing, and provides a streak free, glossy finish. Furthermore, it can be applied to the wet surface to dry and wax the surface in one step.
It is another object of the present invention to provide a composition that can be applied to multiple surfaces such as automotive surfaces. Automotive surfaces include painted, plastic, chrome, glass, and other surfaces of cars, motorcycles, trucks, boats, as well as other vehicles. Furthermore the present invention can be applied to other hard surfaces around the home and garage including furniture articles and glass surfaces.
It is another object of the present invention to provide a composition where the organic phase which may include wax, UV protectants, etc. has a specific gravity substantially close to that of the aqueous phase. This will substantially reduce the settling or separation of the organic phase from the aqueous phase.
It is another object of the present invention to provide a composition that is substantially free of solvents therefore it is environmentally friendly as well as consumer friendly.
It is another object of the present invention to provide a composition that can be delivered in aerosol or pump spray containers. The described invention would greatly reduce the effort needed to apply these materials to the previously mentioned surfaces.
The foregoing objects and any other that become apparent were accomplished by the discovery of a method of turning emulsions/dispersions into suspensions, by neutralizing the surfactants used in making the emulsion/dispersion. One way to accomplish this is by creating an ionic emulsion of one or more film forming polymers, such as wax or urethane polymers, using an ionic surfactant, then, neutralizing it with a counterionic surfactant with a polarity opposite to that of the said ionic surfactant. Another method of making suspensions is to combine two or more ionic emulsions/dispersions where the surfactants in the emulsions/dispersions have opposite charges. For example one emulsion/dispersion containing mainly anionic surfactants is combined with another emulsion/dispersion containing mainly cationic surfactants. Other surfactants such as nonionics may also be present at levels that would not interfere with formation of the suspension. Most surprisingly, the new suspensions show strong affinity towards any surface that is less polar than water such as automotive painted surfaces and glass.
The present invention provides an aqueous protective composition for automotive surfaces and the like, comprising at a minimum wax, UV protectant, surfactant, and water.
In one aspect of the present invention, an aqueous protective composition comprising at least one wax, at least one UV protectant, at least one surfactant, and between 40% and 99.8% water is disclosed. In yet another aspect of the present invention, an aqueous protective composition comprising at least one wax, at least one UV protectant, at least one surfactant, at least one silicone compound and between 40% and 99.8% water by weight is disclosed. The silicone compound can include, but is not limited to amino-functional silicones, dialkyl silicones, silicone resins, silicone waxes, hydrocarbon silicone copolymers, halogenated-hydrocarbon silicone copolymers, volatile silicones, silanes, silanols, reactive silicones, silicone spreading additives, and combinations thereof. Other embodiments of the present invention may also include film-forming resins, fluorinated resins and surfactants, one or more preservatives, such as bactericides, oleosoluble colorants, as well as other additives, such as thickening agents.
Yet another aspect of the present invention relates to a method of protecting a substrate from sources of environmental damage. The sources of environmental damage can include for example UV rays, water spotting, rain and acid rain, inorganic salts, dirt and grime, road tar, bird droppings and other environmental contaminants. According to one method of the present invention, a substrate is coated with a continuous layer of the protectant composition. The protectant of the present invention may be used on automotive surfaces, boats, RVs, motorcycles, and for almost any hard surface found around the home or garage including glass surfaces. The protectant film provides low surface energies to promote beading, which will reduce spotting brought about by water standing on surfaces. One embodiment of the present invention may be applied by pump spray application or aerosol.
The total wax used in this composition can vary from 0.01% to 50% of the total weight of the composition and more preferably from 0.1 to 10% of the total weight of the composition. At least one of the waxes in this composition melts between 40C. and 120C. and can be selected from natural waxes, modified natural waxes, synthetic waxes, or any combination of these. The UV protectant used in this composition can be UVA absorbers, UVB absorbers, UVAandB absorbers, free-radical scavengers, light stabilizers, or any combination of these. The level of UV absorbers can vary from 0% to 15% of the total weight of the composition and more preferably from 0% to 5% of the total weight of the composition. The level of light stabilizers can vary from 0% to 15% of the total weight of the composition and more preferably from 0% to 5% of the total weight of the composition. The total level of silicone oils can vary from 0% to 20% of the total weight of the composition and more preferably from 0% to 5% of the total weight of the composition. The total weight of amino-functional silicones can vary from 0% to 20% of the total weight of the composition and more preferably from 0% to 5% of the total weight of the composition. The surfactant(s) can be anionic, nonionic, cationic, zwitterionic, amphoteric, wetting agents, or any combinations of these. More preferably, combinations of cationic and anionic surfactants are used in a ratio of 1:50-50:1. Mixtures of cationic and anionic surfactants in a ratio of 1:5-5:1 are still more preferred. Small amounts of nonionic or other surfactants may also be present to offer minor advantages. The total weight of the surfactants can vary from 0.1% to 25% of the total weight of the composition and more preferably from 0.1% to 10% of the total weight of the composition. The total weight of the preservatives (bactericide) can vary from 0% to 10% of the total weight of the composition and more preferably from 0% to 4% of the total weight of the composition. The level of water can vary from 40% to 99.8% of the total weight of the composition and more preferably from 75% to 99.8% of the total weight of the composition. Additional benefits may be obtained by incorporating fluorinated polymers, and/or fluorinated film forming resins and/or fluorinated wetting agents.
The waxes are natural substances (animal or vegetable) or synthetic materials solid at ambient temperature (20C.-25C.). They are insoluble in water, soluble in oils and are capable of forming a water repellant film. The wax or waxes constituting the wax mixture are selected from among Carnauba wax, Candelilla wax and Alfa wax, Montan wax, polyethylene wax, paraffin wax, oxidized paraffin wax, ozokerite, vegetable waxes such as olive tree wax, rice wax, hydrogenated jojoba wax or absolute waxes of flowers such as the essential wax of cassis flower sold by Bertin (France); animal waxes such as beeswax, or modified beeswax (cerabellina); other waxes or primary waxy materials: marine waxes such as that sold by Sophim under the name xe2x80x9cM82(trademark)xe2x80x9d natural or synthetic ceramides or polyethylene waxes. Other synthetic waxes include silicone waxes including but not limited to xe2x80x9cSilky Wax 10(trademark)xe2x80x9d sold by Dow Corning. Synthetic waxes may include clear synthetic waxes including but not limited to xe2x80x9cUniclear 80(trademark)xe2x80x9d and xe2x80x9cUniclear 80V(trademark)xe2x80x9d sold by Arizona Chemical Company. The vegetable waxes of Camauba (extract of Copemrica Cerifera), of Candelilla (extract of Euphobies Cerifera and Pedilantus pavonis) and of Alfa (extract of Stipa tenacissima), are commercial products. The mixture of waxes can then be combined with one or more additives including but not limited to mineral oils such as paraffin oil, fluid silicone oils, silicone resins, amino-functional silicones, fluorinated silanes and silicones, fluorinated oils and waxes, petrolatum and lanolin.
The mixture of waxes can also be combined with one or more UV absorbers including UVA absorbers and/or UVB absorbers and/or UVAandB absorbers and/or light stabilizers. There are a number of manufacturers of these UV protectants including but not limited to Ciba, Clariant, Creanova, and Celenase to name a few. One example of a UV absorber is iso-octyl-3-(3-(2H-benzotriazol-2-yl)-5-tertiarybutyl-4-hydrxyphenylpropionate (CASRN 127519-17-9). An example of hindered amine light stabilizers can be Bis(1,2,2,6,6-pentamethy-4-piperdinyl)-sebacate (CASRN 41556-26-7)), or -(methyl)-8-(1,2,2,6,6-pentamethy-4-piperdinyl)-sebacate (CASRN 82919-37-7). A synergistic combination of the above UVA absorber and hindered amine light stabilizers is sold by Ciba as xe2x80x9cTinuvin 5055(trademark)xe2x80x9d. For compositions specific to glass, mainly UV absorbers are incorporated.
The use of surfactants as emulsifying agents in the preparation of wax emulsion/dispersions is known. The production of the emulsion/dispersion can be carried out using anionic, nonionic, and/or cationic surfactants, in a known manner. The anionic surfactants employed are principally salts of fatty acids (for example alkaline salts or organic salts such as amine salts), the said fatty acids having, for example, from 12 to 18 carbon atoms and being able to have a double bond as in the case of oleic acid, alkaline salts or organic base salts of alkyl-sulfuric and alkyl sulfonic acid having 12 to 18 carbon atoms, alkyl-arylsulfonic acids whose alkyl chain contains from 6 to 18 carbon atoms, the aryl group being, for example, a phenyl group. They are also ether-sulfates, in particular the sulfonation products of fatty alcohols and polyalkoxylated alkyl phenols in which the aliphatic chain contains from 6 to 20 carbon atoms and the polyalkoxylated chain from 1 to 30 oxyalkylene units, in particular oxyethylene, oxypropylene or oxybutylene. All these anionic surfactants are well known and many of them are commercial products.
The nonionic surfactants are principally polyalkoxylated and/or polyglycerolated surfactants. They are principally polyalkoxylated and/or polyglycerolated fatty acids or arnides of fatty acids; polyalkoxylated and/or polyglycerolated fatty alcohols or alkylphenols; polyalkoxylated and/or polyglycerolated esters of fatty acids and polyols; polyalkoxylated and/or polyglycerolated 1,2- or 1,3-alkanediols or alkenediols; polyalkoxylated and/or polyglycerolated alkylethers of 1,2- or 1,3-alkanediols or alkenediols. For example, the fatty acids or alcohols, optionally unsaturated, have 12-24 carbon atoms, the alkyl chain of the alkylphenols has 6 to 16 carbon atoms, the alkanediols or alkenediols have from 9 to 24 carbon atoms, the alkyl of the alkyletmers h as from 4 to 20 carbon atoms, and the number o f oxyalkylene units or of (CH2CHOHCH2O) units can range from 2 to 40. The polyalkoxylated nonionic derivatives are principally polyoxyethylenated, optionally polyoxypropylenated derivatives. The polyalkoxylated fatty acids are commercial products, principally those sold under the trade name xe2x80x9cMYRJ(trademark)xe2x80x9d by Atlas. The polyoxyethylenated esters of fatty acids and polyols for which the polyol is sorbitol are known products (Polysorbate and products sold under the trade name xe2x80x9cTWEEN(trademark)xe2x80x9d by Atlas). When the polyol is glycerol, products sold by Goldschmidt under the trade name xe2x80x9cTAGAT(trademark)xe2x80x9d can be used. The polyoxyethylenated fatty alcohols are commercial products, principally those sold under the mark xe2x80x9cBRIJ(trademark)xe2x80x9d by Atlas. Other useful nonionic surfactants are, for example: triglycerol alkylcarbamates having the general formula: Rxe2x80x94NHCOOCH(CH2OCH2CHOHCH2OH)2, wherein R represents a saturated or unsaturated alkyl group having 10-20 carbon atoms. Oxyethylenated or propoxylated derivatives of lanolin alcohols, lanolin fatty acids, or mixtures thereof. Such surfactants are sold by Amerchol under the trade name xe2x80x9cSOLULAN(trademark)xe2x80x9d.
The cationic surfactants can be chosen from quaternary ammonium derivatives such as xe2x80x9cARQUAD 16-50(trademark)xe2x80x9d, xe2x80x9cARQUAD 18-50(trademark)xe2x80x9d, xe2x80x9cARQUAD T-50(trademark)xe2x80x9d, xe2x80x9cARQUAD 2C-75(trademark)xe2x80x9d, xe2x80x9cETHOQUAD c/12(trademark)xe2x80x9d, and xe2x80x9cETHOQUAD o/12(trademark)xe2x80x9d, or the amine salts like xe2x80x9cArmid O(trademark)xe2x80x9d, xe2x80x9cArmid HT(trademark)xe2x80x9d, and xe2x80x9cArmak HT(trademark)xe2x80x9d sold by Akzo Nobel, as well as many others.
It is also possible to commercially obtain wax emulsions/dispersions. There can be employed, for example, the wax sold under the trade name xe2x80x9cMichem Lube 160(trademark)xe2x80x9d and xe2x80x9cMichem Lube 160(trademark)xe2x80x9d from Michelman which contain Camauba wax in combination with anionic emulsifying agents, xe2x80x9cMichem Lube 180(trademark)xe2x80x9d which contains Camauba and paraffin waxes, in combination with anionic emulsifying agents xe2x80x9cMichem Lube 188(trademark)xe2x80x9d which contains Camauba and microcrystalline waxes, in combination with anionic emulsifying agents xe2x80x9cMichem Lube 110(trademark)xe2x80x9d, which contains Camauba and polyethylene waxes, in combination with anionic emulsifying agents. Examples of wax emulsion/dispersions, which contain nonionic surfactants, include xe2x80x9cMichem Lube 156(trademark)xe2x80x9d and xe2x80x9cMichem Lube 156(trademark)xe2x80x9d. It is also possible to prepare wax emulsion/dispersions or microdispersions by using commercial mixtures of self-emulsifiable waxes containing the wax and surfactants. There can be employed, for example, the wax sold under the trade name xe2x80x9cCIRE AUTO LUSTRANTE OFR(trademark)xe2x80x9d by Tiscco, which contains Camauba and paraffin waxes, in combination with nonionic emulsifying agents, or the self-emulsifiable wax sold under the trade name xe2x80x9cCERAX A. O. 28/B(trademark)xe2x80x9d by La Ceresine, which contains Alfa wax in combination with a nonionic emulsifying agent. These commercial mixtures permit the preparation of wax emulsion/dispersions or microdispersions by the addition of water in accordance with the process described above.
There can also be employed ready-to-use wax microdispersions, available commercially as the xe2x80x9cSERIE SL SLIPAID(trademark)xe2x80x9d products of Daniel Products Company, or even xe2x80x9cAQUACER(trademark)xe2x80x9d products of Cerachemie. The wax dispersions or microdispersions are dilutable with water without interfering with the stability of the dispersion or microdispersion. Consequently they can be provided in the form of concentrated compositions the proportions of the ingredients of which can be adjusted to a desired value by the simple addition of water. In the case of ready-made wax emulsion/dispersions or microdispersions, dispersions of the UV protectants and UV light stabilizers can be blended with the wax emulsion/dispersion. An example of water dispersion of UV absorbers are xe2x80x9cSanduvor VSU(trademark)xe2x80x9d and xe2x80x9cSanduvor 3225(trademark)xe2x80x9d for UV absorbers/UV light stabilizers from Clariant Corporation.
The silicones can also be obtained from several sources including but not limited to GE, Dow Corning, and Wacker. The silicone products can also be in the form of straight oils or water emulsions. The examples used here will be those manufactured by Dow Coming while there are many other equivalent products. Where silicone fluids are used, those having a viscosity ranging principally between 0.65 and 100,000 centistokes, preferably between 5 and 5,000 centistokes, are used. An example of a preferred silicone fluid in this range is xe2x80x9cDC200-350cs(trademark)xe2x80x9d fluid. An example of a nonionic water emulsion of this silicone fluid is xe2x80x9cDC346(trademark)xe2x80x9d emulsion.
The organosilicon resin can be a single resin or a mixture of different resins. Generically, it is an organosilicon resinous copolymer which includes SiO4/2 units with one or more units selected from the group consisting of R3SiO1/2 units, R2SiO2/2 units, and RSiO3/2 units, in a molar ratio such that the number average molecular weight of the resinous copolymer is 1,200-10,000. R is a hydrocarbon group such as alkyl radicals with 1-6 carbon atoms; aryl radicals such as phenyl, tolyl, and xylyl; alkenyl radicals such as vinyl and allyl; and trifluoropropyl radicals. The resin can be used alone or mixed with 1-60% by weight of a linear or branched siloxane fluid of the formula R3SiO(R2SiO)nSiR3 in which R has the meaning defined above. n is 1-100,000, which includes siloxane fluids with viscosities up to 2,500,000 centistokes. For example, a value 500 for n, provides a fluid with a viscosity of 10,000 centistokes.
Organosilicon polymer or resin can also be a siloxane resin copolymer including R3SiO1/2 units and SiO4/2 units in a mole ratio such that the number average molecular weight is 1,200 to 10,000. Preferably, the mole ratio is 0.7:1.0, and the number average molecular weight is 5,000. R is previously defined. The resin may contain R2SiO2/2 units and RSiO3/2 units. It may also contain 2.5 weight percent silicon bonded OH groups.
An amino-functional polysiloxane contains highly polar pendant aminoalkyl modifying groups that enhance the durability of films formed by polysiloxanes, and promote adhesion of films to a variety of substrates. Particularly preferred amino-functional polysiloxanes include reactive and non-reactive hydrolyzable and non-hydrolyzable derivatives which are wholly, or in part, terminally substituted with aminopropyl, aminobutyl, or diamino pendant chains. The amino-functional polysiloxane has the formula: R3-z xe2x80x2QzSiO(R2xe2x80x2SiO) x(Rxe2x80x2QSiO)ySiQzR3-z where Rxe2x80x2 is an alkyl group of 1-4 carbons or a phenyl group, provided that at least 50 percent of the total number of Rxe2x80x2 groups are methyl. Q is an amine functional xe2x80x94Rxe2x80x3Z. Rxe2x80x3 is a divalent alkylene radical of 3-6 carbon atoms, and Z is a monovalent radical such as xe2x80x94NR2xe2x80x2xe2x80x3 or xe2x80x94NRxe2x80x2xe2x80x3 (CH2) nNR2xe2x80x2xe2x80x3. Rxe2x80x2xe2x80x3 is hydrogen or an alkyl group of 1-4 carbon atoms. n is 2-6. z is 0 or 1. x is 25-3000. y is 0-100 when z is 1 but y is 1-100 when z is 0. In all cases, y is not greater than one tenth the average value of x. Suitable Rxe2x80x2 groups are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and phenyl, provided that at least 50% of the Rxe2x80x2 groups are methyl. Alkylene radicals Rxe2x80x3 include trimethylene, tetramethylene, pentamethylene, xe2x80x94CH2CHCH3CH2xe2x80x94, and xe2x80x94CH2CH2CHCH3CH2xe2x80x94. Siloxanes where Rxe2x80x3 is trimethylene or an alkyl substituted trimethylene radical such as xe2x80x94CH2CHCH3CH2xe2x80x94 are preferred. Alkyl groups represented by Rxe2x80x2xe2x80x3 include methyl, ethyl, propyl, isopropyl, butyl, and isobutyl. Useful Z radicals include unsubstituted amine radicals such as xe2x80x94NH2, alkyl substituted amine radicals such as xe2x80x94NHCH3, NHCH2CH2CH2CH3 and xe2x80x94N(CH2CH3)2; and aminoalkyl substituted amine radicals such as xe2x80x94NHCH2CH2NH2, xe2x80x94NH(CH2)NH2, and xe2x80x94NH2CH2CH2N(CH3)2. When z is zero, the polymer has only pendent amine functional substituents in the chain. When z is one, the polymer may have only terminal amine functional substituents, or both terminal and pendent amine functional substituents in the chain. Preferably, x varies from 25-100. y varies from 0-100 when z is one and 1-100 when z is zero. Most preferably, the sum of x+y is 50-500. An example of an amino-functional emulsion includes but is not limited to xe2x80x9cDC929(trademark)xe2x80x9d sold by Dow Corning. An example of reactive amino-functional silicone oil includes but is not limited to xe2x80x9cDC536(trademark)xe2x80x9d oil sold by Dow Corning, which contains amino and methoxy functional groups.
Other film-forming polymers useful in the composition of the invention can be anionic, cationic, nonionic or amphoteric polymers. There can be employed synthetic polymers or polymers of natural origin, chemically modified or not modified. Mention can principally be made of cationic polymers, which are polymers of the polyamine, polyaminopolyarnide or quaternary polyammonium type in which the amine or ammonium group is a part of the polymer chain or is linked to it; they generally have a molecular weight ranging from 500 to 3,000,000. As useful cationic film-forming polymers, mention can be made, for example, of: (1) vinylpyrrolidone/dialkylaminoalkyl acrylate or methacrylate copolymers (quatemized or not), such as those sold under the trade names xe2x80x9cGAFQUAT(trademark)xe2x80x9d by GAF Corp., as for example, xe2x80x9cCopolymer 845(trademark)xe2x80x9d, xe2x80x9cGAFQUAT 734(trademark)xe2x80x9d or xe2x80x9c735(trademark)xe2x80x9d, (2) cellulose ether derivatives having quaternary ammonium groups and principally polymers sold under the designations xe2x80x9cJR(trademark)xe2x80x9d, such as xe2x80x9cJR 125(trademark)xe2x80x9d, xe2x80x9cJR 400(trademark)xe2x80x9d, xe2x80x9cJR 30M(trademark)xe2x80x9d, and xe2x80x9cLR(trademark)xe2x80x9d, such as xe2x80x9cLR 400(trademark)xe2x80x9d and xe2x80x9cLR 30(trademark)xe2x80x9d by Union Carbide Corp., cationic cellulose derivatives such as xe2x80x9cCELQUAT L200(trademark)xe2x80x9d and xe2x80x9cCELQUAT H 100(trademark)xe2x80x9d, which are sold by National Starch or those sold by Akzo Nobel under the designation xe2x80x9cLEOGARD GP(trademark)xe2x80x9d,; (3) cationic polysaccharides xe2x80x9cJAQUAR C135(trademark)xe2x80x9d sold by Meyhall; (4) cationic polymers containing alternate units of the formula: xe2x80x94Axe2x80x94Zxe2x80x94, wherein A represents a radical containing two amine functions and the Z groups represent at least one bivalent radical; (5) cyclopolymers such as the homo- and copolymers of dimethyl diallylammonium chloride sold under the designation xe2x80x9cMERQUAT(trademark)xe2x80x9d by Merck; (6) the quaternized vinylimidazolium-vinylpyrrolidone copolymers such as those sold under the trade name xe2x80x9cLUVIQUAT FC(trademark) or HM(trademark)xe2x80x9d by BASF.
The anionic film-forming polymers are polymers having anionic groups, in particular carboxylic and/or sulfonic groups. The preferred anionic polymers employed in the compositions of this invention are selected principally from among: (1) the homo- or copolymers of acrylic or methacrylic acids or their salts and their esters and in particular the products sold under the trade names xe2x80x9cVERSICOL F(trademark)xe2x80x9d or xe2x80x9cVERSICOL K(trademark)xe2x80x9d by Allied Colloid, xe2x80x9cULTRAHOLD 8(trademark)xe2x80x9d by Ciba-Geigy, the copolymers of acrylic acid and acrylamide sold under the form of their sodium salt under the designation xe2x80x9cRETEN TM(trademark)xe2x80x9d by Hercules, sodium polymethacrylate sold under the designation xe2x80x9cDARVAN No 7(trademark)xe2x80x9d by Vanderbilt, the sodium salts of polyhydroxycarboxylic acids, sold under the trade name xe2x80x9cHYDAGEN F(trademark)xe2x80x9d by Henkel; (2) copolymers derived from crotonic acid and their esters; (3) polymers or copolymers derived from maleic, fumaric or itaconic acids or anhydrides with vinylic or phenylvinylic or acrylic derivatives, these polymers being able to be esterified. Among these polymers, mention can be made of the polymers sold under the designations xe2x80x9cGANTREZ(trademark)xe2x80x9d by the GAF Corporation or xe2x80x9cEMA (trademark)xe2x80x9d by Monsanto. Polymers also belonging in this class are the copolymers of maleic, citraconic or itaconic anhydrides and an allylic or methallylic ester having optionally an acrylamide or methacrylamide group in their chain, monoesterified or monoamidified; (4) useful polymers having sulfonic groups in accordance with the invention are selected principally from among: salts of polystyrene sulfonic, polyacrylamide sulfonic salts, or polyester salts such as those sold under the trade name xe2x80x9cPOLYMER EASTMAN AQ(trademark)xe2x80x9d by Kodak.
The amphoteric film-forming polymers useful in the compositions of the invention are aprincipally polymers having M and Mxe2x80x2 units statistically distributed in the polymer chain, where M represents at least one unit derived from a monomer having at least one basic nitrogen atom and Mxe2x80x2 represents at least one unit derived from an acid monomer having one or more carboxylic or sulfonic groups, or even M and Mxe2x80x2 can represent groups derived from zwitterionic monomers of carboxybetaine. M and Mxe2x80x2 can also represent a cationic polymer chain having secondary, tertiary or quaternary amine groups, in which at least one of the amino groups has a carboxylic or sulfonic group linked by the intermediary or a hydrocarbon chain, or even M and Mxe2x80x2 are part of a chain of a polymer having an ethylene alpha-, beta dicarboxylic unit of which one of the carboxylic groups has reacted with a polyamine having one or more primary or secondary amine groups. Mention can be made, for example, of: (1) polymers or copolymers having units derived: (a) from at least one monomer selected from among the acrylamides or methacrylamides, substituted at the nitrogen by an alkyl radical, (b) from at least one acid monomer containing one or more reactive carboxylic groups, and (c) from at least one basic comonomer such as esters having a primary, secondary, tertiary or quaternary amine substituent of acrylic and methacrylic acids and the quatemrization products of dimethylaminoethyl methacrylate with dimethyl or diethyl sulfate. As compounds representative of this class mention can be ma de of xe2x80x9cAMPHOMER(trademark)xe2x80x9d sold by Natural Starch; (2) polymers derived from chitosan; (3) copolymers of diallyl dialkyl (C1-C4) ammonium/acrylic acid such as the product sold under the trade name xe2x80x9cMERQUAT 280(trademark)xe2x80x9d by Merck which is a copolymer of diallyl dimethyl ammonium chloride/acrylic acid.
The nonionic film-forming polymers useful in the composition s of the invention are principally: (1) the homo- and/ or copolymers of vinylpyrrolidone such as the polyvinylpyrrolidone/vinyl acetate copolymer sold under the trade name xe2x80x9cPVP/PVA S-630(trademark)xe2x80x9d by GAF, or the trade name xe2x80x9cLUVISKOL(trademark)xe2x80x9d by BASF; (2) the nonionic vinylic homopolyners or copolymers such as polyvinyl alcohol sold under the trade name xe2x80x9cMOWIOL 4088(trademark)xe2x80x9d by Hoechst; (3) derivatives of polyaspartic acid; or even (4) polyglycols such as polyethylene glycols. Mention can also be made of the family of polyurethanes in solution or anionic, cationic or nonionic dispersions.
The dye must be an oil soluble dye in order for the color of the dye to be retained in the present protectant composition. It cannot be a water-soluble dye. The four dye colors are each used in a different colored embodiment of the protectant of this invention. Each colored embodiment can be used in a range of colored surfaces. In particular, a colored embodiment of the present application can be used in several different shades. For example, the red colored embodiment can be used in about five to about ten different shades of a red surface. The four preferred dyes are green, black, red and blue colorings. The black dye is preferably from the azine dye chemical family and is known as Nigrosine base N or solvent black 7 CASRN 8005-02-5. The red dye is preferably from the bis-azo dye chemical family and has the formula C25H22N4O. The blue dye is preferably from the anthraquinone dyestuff chemical family and has the chemical formula C30H42N2O2. The dye is present in an amount between about 0.0005 and about 2.0 percent by weight of the total protectant composition.
The composition can be thickened if des i red. Among the thickeners useful in the compositions of the invention mention can also be made of cellulosic and saccharidic polymers such as hydroxymethyl cellulose, carboxymethyl cellulose, hydroxybutyl cellulose, hydroxypropyl cellulose, and more particularly, hydroxyethyl cellulose, in particular the products sold under the trade name xe2x80x9cNATROSOL(trademark)xe2x80x9d by Hercules or xe2x80x9cCELLOSIZE(trademark)xe2x80x9d by Union Carbide, methylhydroxypropyl cellulose, in particular the products sold under the trade name xe2x80x9cMETHOCEL(trademark)xe2x80x9d by Dow Chemical or heterobiopolysaccharides such as for example, xanthan gums sold under the marks xe2x80x9cKELTROL(trademark)xe2x80x9d and xe2x80x9cKELZAN(trademark)xe2x80x9d by Kelco, xe2x80x9cRHODOPOL(trademark)xe2x80x9d and xe2x80x9cRHODIGEL(trademark)xe2x80x9d by Rhone Poulenc, or xe2x80x9cACTIGUM(trademark)xe2x80x9d by Ceca/Satia, gum arabic, guar gum, Karoya gum, alginates and carraghenates, hyaluronic acid and its derivatives. Other film-forming polymers can be selected from among hydroxyethyl cellulose, gum arabic, polyvinylpyrrolidone, cationic cellulose derivatives, sodium polymethacrylate and keratin hydrolyzates. Other known thickening agents can be employed and are selected, for example, from among polyacrylic acids crosslinked by a polyfunctional agent such as the products sold under the designation xe2x80x9cCARBOPOL(trademark)xe2x80x9d by Goodrich, such as xe2x80x9cCARBOPOLS 910 (trademark), 934 (trademark), 934 (trademark), 940 (trademark), 941 (trademark), 980 (trademark), 1342(trademark), EZ1(trademark), EZ2(trademark)xe2x80x9d, natural or modified clays such as the xe2x80x9cLAPONITES(trademark)xe2x80x9d, of Laporte or xe2x80x9cVEEGUM(trademark)xe2x80x9d, of Vanderbilt or polyurethanes.
Examples of fluorinated polymers include but are not limited to fluorochloroamide polymers, polytrifluorochloroethylene, fluorochloroalkyl polymers, fluorochloroacrylic polymers, chlorofluorosilicone polymers and the like. The preferred halofluorinated polymers are the fluorochloroamide polymers sold under the trademark xe2x80x9cFLUOROLINK 418(trademark)xe2x80x9d sold by Ausimont, U.S.A. Others include xe2x80x9cFLUOROLINK (201)(trademark)xe2x80x9d a chlorofluoro phosphate ester, xe2x80x9cFLUOROLINK 407(trademark)xe2x80x9d a chlorofluorosilane and xe2x80x9cFLUOROLINK 300(trademark)xe2x80x9d a chlorofluorocarboxylic acid. The spreading (wetting) additives can be fluorinated derivatives such as those sold by 3M under the name xe2x80x9cFLUORAD(trademark)xe2x80x9d and those sold by Dupont under the name xe2x80x9cZonyl(trademark)xe2x80x9d, or copolyol dimethicone surfactants having a high HLB available from Dow Coming, Goldschmidt, etc.
One or more preservatives (bactericide) can also be incorporated in the composition of this invention. Several different manufacturers exist that provide preservatives (bactericide) including but not limited to xe2x80x9cDowicil(trademark)xe2x80x9d products from Dow Chemical and xe2x80x9cKathon(trademark)xe2x80x9d products from Rohm and Haas.
The compositions according to the invention are obtained by forming an emulsion. Generally, these compositions are obtained by a process principally characterized by the fact that the wax and the emulsifying agent(s) are heated to a temperature greater than the melting temperature of the wax and not greater than 100 degree Celsius, optionally in the presence of a portion of the water, until the wax is completely melted; the water is also heated to a temperature at least equal to the said temperature employed to melt the wax and then the melted wax can be added to the water, or the remainder of water is progressively added to the wax, while stirring, until a wax emulsion is formed in a continuous aqueous phase, and then permitting the whole to cool to ambient temperature. Also, the surfactant(s) can be divided into the water phase and the oil phase before combining the two. A stable wax dispersion/emulsion is thus obtained. The emulsifier/surfactant used is preferably anionic or cationic. More preferably anionic surfactants are used for preparation of the wax emulsion.
The liposoluble ingredients, for example, UV absorbers/light stabilizers, are generally added to the wax prior to the formation of the dispersion. These liposoluble ingredients can alternatively be added as a dispersion to the wax dispersion keeping the ionic character the same. For example an anionic dispersion of the UV absorbers/light stabilizers is added to anionic wax dispersions while a cationic dispersion of the UV absorbers/light stabilizers is added to cationic wax dispersions. Nonionic dispersions of the UV absorbers/light stabilizers can be combined either with anionic or cationic wax dispersion. The water-soluble ingredients can be added in the water used to produce the dispersion, or in the finally obtained wax dispersion. Also, the secondary ingredients optionally present in the composition are added either to the starting products or to the finished composition.